Photodissociation of ICN-(CO2)n, n = 0-18, with 500-nm excitation is investigated using a dual time-of-flight mass spectrometer. Photoabsorption to the 2Π1/2 state is detected using ionic-photoproduct action spectroscopy; the maximum absorption occurs around 490 nm. Ionic-photoproduct distributions were determined for ICN-(CO2)n at 500 nm. Following photodissociation of bare ICN- via 430-650 nm excitation, a small fraction of CN- is produced, suggesting that nonadiabatic effects play a role in the photodissociation of this simple anion. Electronic structure calculations, carried out at the MR-SO-CISD level of theory, were used to evaluate the potential-energy surfaces for the ground and excited states of ICN-. Analysis of the electronic structure supports the presence of nonadiabatic effects in the photodissociation dynamics. For n ≥ 2, the major ionic photoproduct has a mass corresponding to either partially solvated CN - or partially solvated [NCCO2]-.
ASJC Scopus subject areas
- Physics and Astronomy(all)
- Physical and Theoretical Chemistry